CN107954974A - A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate - Google Patents

A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate Download PDF

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CN107954974A
CN107954974A CN201711275937.XA CN201711275937A CN107954974A CN 107954974 A CN107954974 A CN 107954974A CN 201711275937 A CN201711275937 A CN 201711275937A CN 107954974 A CN107954974 A CN 107954974A
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carbon dioxide
manganese
catalyst
cyclic carbonate
chemical recycling
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张晓峰
王娜
陈振宇
曹毅
王延伟
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Henan Institute of Engineering
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J35/19—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/64—Oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/22—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese

Abstract

The invention discloses a kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, raw material is used as by the use of carbon dioxide and epoxides, to be conjugated manganoporphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is co-catalyst, in the case where normal temperature and pressure is solvent-free, efficient green catalytically synthesizing cyclic carbonate ester is realized.The major advantage of this method is that method for preparing catalyst is simple, and cost is low, and catalytic activity is high, and structural behaviour is stablized, easily recycling, repeats and utilizes；Reaction condition is gentle, speed is fast and safe operation, suitable for large-scale industrial production.

Description

A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of manganese-based catalyst chemical recycling of carbon dioxide prepares ring-type The method of carbonic ester.
Background technology
With the progress of the development human civilization of society, especially industrial great development with rapid changepl. never-ending changes and improvements, for fossil energy The consumption requirements in source increasingly increase.A large amount of with fossil fuel use, and the concentration of carbon dioxide quickly raises, and becomes a kind of master Greenhouse gases are wanted, cause a series of environment and ecological problem.Meanwhile carbon dioxide is used as a kind of widely distributed, rich reserves, honest and clean Valency is easy to get, is renewable, is nontoxic, one resource of non-flammable preferable carbon.No matter from the angle that environmental protection or renewable resource utilize Degree considers that the research in terms of the capture and chemical conversion of carbon dioxide is all of great significance.Using carbon dioxide as Material synthesis Organic carbonate is exactly an exemplary of its recycling, has been realized in industrialized production at present.
Organic carbonate is a kind of green chemical with characteristics such as higher boiling, low-steam pressure, low toxicities, has been widely used in The multiple fields such as solvent, detergent, lithium battery electrolytes, fuel additive.Organic carbonate can be divided into linear carbonate And cyclic carbonate.Wherein cyclic carbonate is widely used as the electrolyte of lithium battery, with the fast development of new energy, market pair It is increasing in the demand of high-quality cyclic carbonate.
From the perspective of Green Chemistry and sustainable development, using carbon dioxide and epoxides as Material synthesis carbonic ester Provide a kind of safe and clean, sustainable, high atom economy new way.Current industrialized carbon dioxide and ring The process that oxygen prepares cyclic carbonate mainly has two kinds of catalyst system and catalyzings：Polyethylene glycol/potassium iodide system and quaternary ammonium salt system.The former Iodine can be generated during the reaction, causes finished product to turn to be yellow, and product quality declines；And the pressure that the latter needs during the reaction Power is higher, to the security of production operation, more demanding, the equipment cost height for performance that equipment is pressure-resistant.
At present, with CO2It is raw material with cyclic carbonate, in the reaction system of synthesizing annular carbonate, has developed A series of catalyst, as quaternary ammonium salt, quaternary alkylphosphonium salts, organic base, ionic liquid, metal oxide, metal complex, feature are organic Polymeric material and metalloporphyrin etc..2013, the research group of Deng et al. was using salen Al/Co and three ethynylbenzenes to be single Body, by Sonogashira coupling reactions, is prepared for microporous polymer catalyst Al-CMP and Co-CMP, in the reaction system In achieve preferable catalytic effect, and the just desirable good yield under normal temperature and pressure conditions, while catalyst may be used also Recycling [Nat.Commun., 2013,4,1-7].2016, Xiao Fengshou taught seminar with tetravinyl Cob altporphyrin For monomer, by the method for radical polymerization, catalyst Co/POP-TPP is made, at 29 DEG C, when pressure is 0.1MPa, reaction 24h, achieve it is satisfied as a result, catalyst can circulation and stress use, and by low concentration CO2As research object, have Certain industrial application value [J.Catal., 2016,338,202].
The content of the invention
The technical problems to be solved by the invention are deposited inefficient in a mild condition for the current reaction system Problem, there is provided a kind of synthesis step is simple, raw material is cheap and easy to get, high catalytic efficiency, the stable heterogeneous catalyst easily recycled, normal Under normal temperature and pressure, condition of no solvent, efficient catalytic is converted into cyclic carbonate, can be widely applied to field of industrial production.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, original is used as using carbon dioxide and epoxides Material, to be conjugated manganoporphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is co-catalyst, in normal temperature and pressure Under solvent-free, 12-48h to be reacted, has synthesized cyclic carbonate in high yield, heterogeneous catalyst separation is simple, washable recycling, and It can realize and repeatedly use.
The conjugation manganoporphyrin capillary copolymer material uses Scholl coupling reactions, using manganese tetraphenylporphyrin to be single Body, uses the anhydrous AlCl of low cost3Catalyst preparation obtains, its structural formula is as follows：
。
The epoxide is propylene oxide, epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, benzene Base glycidol ether or cyclohexene oxide.
The dosage of the active component of the heterogeneous catalyst is 0.2~0.5mol% of epoxide dosage.
The dosage of the co-catalyst is 3.6~7.2mol% of epoxide.
The conjugation manganoporphyrin capillary copolymer material can be replaced with conjugation manganoporphyrin bibenzyl amine capillary copolymer material, The conjugation manganoporphyrin bibenzyl amine capillary copolymer material uses Scholl coupling reactions, using manganese tetraphenylporphyrin and benzylamine as Monomer, uses anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows：
。
Beneficial effects of the present invention：1) present invention utilizes and is conjugated manganoporphyrin/conjugation manganoporphyrin bibenzyl amine microporous polymer material Material and tetra-n-butyl ammonium bromide are realized under normal temperature and pressure conditions, efficient catalytic CO as bicomponent catalyst2And epoxides Synthesizing annular carbonate, saves mass energy, reduces the requirement to press device in production, substantially increases the peace of operation Quan Xing；2) catalyst amount is low, high catalytic efficiency, reaction time are short, product is easily isolated purifying, is operated easy to actual industrial； 3) any organic solvent need not be added, it is environmentally protective；4) catalyst raw material used in is easy to get, cost is low, the quick letter of synthesis It is single.Heterogeneous catalyst separation is simple, washable recycling, and can realize and repeatedly use（More than 20 times）.
Specific implementation method
The present invention is further described in the examples below, but the merely illustrative purposes of discussion of these embodiments, should not be solved It is interpreted as the implementation limitation of the present invention.
Embodiment 1
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.4mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol propylene oxide and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through titanium dioxide Carbon and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining dioxy After changing carbon, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 96%.
Embodiment 2
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.3mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through titanium dioxide Carbon and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining dioxy After changing carbon, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 94%.
Embodiment 3
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.5mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy It is 0.1MPa to change carbon and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining two After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 97%.
Embodiment 4
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.45mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through two Carbonoxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 36h, room temperature cooling, slowly discharges remaining After carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 96%.
Embodiment 5
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.2mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol styrene oxides and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy It is 0.1MPa to change carbon and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining two After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 92%.
Embodiment 6
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.2mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides, lead to It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 24h, room temperature cooling, slowly release is surplus After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 90%.
Embodiment 7
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.3mol%）Catalyst conjugation manganese Porphyrin capillary copolymer material, 12.5mmol cyclohexene oxides and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through two Carbonoxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 12h, room temperature cooling, slowly discharges remaining After carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 91%.
Embodiment 8
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.5mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol propylene oxide and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides, lead to It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 36h, room temperature cooling, slowly release is surplus After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 96%.
Embodiment 9
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.3mol%）Catalyst, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through carbon dioxide and keep the pressure to be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, after slowly discharging remaining carbon dioxide, filtering point Catalyst is separated out, the separation yield for obtaining cyclic carbonate after purification is 92%.
Embodiment 10
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.45mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 96%.
Embodiment 11
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.4mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 94%.
Embodiment 12
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.2mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol styrene oxides and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 90%.
Embodiment 13
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.3mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.675mmol co-catalyst tetra-n-butyl bromines Change ammonium, it is 0.1MPa to be passed through carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 12h, room temperature cooling, delays After the remaining carbon dioxide of On The Drug Release, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 88%.
Embodiment 14
The method that the manganese-based catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into the stainless steel autoclave of 10mL, 50mg is sequentially added（Active component manganese 0.4mol%）Catalyst conjugation manganese Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol cyclohexene oxides and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides, It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 12h, and room temperature cooling, slowly release After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 90%.
The content of active component is on the basis of the dosage of epoxide in above-described embodiment.

Claims (6)

1. a kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, it is characterised in that using carbon dioxide and Epoxides is as raw material, and to be conjugated manganoporphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is urged to help Agent, in the case where normal temperature and pressure is solvent-free, reacts 12-48h, realizes efficient green catalysis carbon dioxide synthesizing annular carbonate.
2. the method that manganese-based catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist In：The conjugation manganoporphyrin capillary copolymer material uses Scholl coupling reactions, using manganese tetraphenylporphyrin as monomer, uses Anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows：
。
3. the method that manganese-based catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist In：The epoxide is propylene oxide, the contracting of epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, phenyl Water glycerin ether or cyclohexene oxide.
4. the method that manganese-based catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist In：The dosage of the active component of the heterogeneous catalyst is 0.2~0.5mol% of epoxide dosage.
5. the method that manganese-based catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist In：The dosage of the co-catalyst is 3.6~7.2mol% of epoxide.
6. the method that cyclic carbonate is prepared according to any manganese-based catalyst chemical recycling of carbon dioxide of claim 1 ~ 5, its It is characterized in that：The conjugation manganoporphyrin capillary copolymer material can use conjugation manganoporphyrin bibenzyl amine capillary copolymer material generation Replace, the conjugation manganoporphyrin bibenzyl amine capillary copolymer material uses Scholl coupling reactions, with manganese tetraphenylporphyrin and benzyl Amine is monomer, uses anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows：
。
CN201711275937.XA 2017-12-06 2017-12-06 A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate Withdrawn CN107954974A (en)

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CN103987714A (en) * 2011-09-21 2014-08-13 国立大学法人冈山大学 Metal porphyrin complex, method for producing same, carbon dioxide immobilization catalyst comprising same, and method for producing cyclic carbonic acid ester.
CN102731766A (en) * 2012-07-24 2012-10-17 中国科学院长春应用化学研究所 Preparation method of aliphatic polycarbonate polyol
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Application publication date: 20180424